1. Field of the Invention
The present invention relates to alkoxyimino-substituted bicyclic derivatives, a process for producing them, agents for controlling diseases and insect pests containing them as an active ingredient, and intermediates of them.
2. Description of the Background
Various compounds usable as agricultural fungicides have been known hitherto. For example, Japanese Patent Unexamined Published Application (hereinafter referred to as xe2x80x9cJ. P. KOKAIxe2x80x9d) No. Hei 4-182461 discloses agricultural fungicides containing alkoxyiminoacetamide compounds as active ingredients. The specific compounds stated -in this patent specification include, for example, 2-methoxyimino-2-[2-(indane-5-yloxymethyl)-phenyl]-acetic acid methylamide (compound No. 20). 
J. P. KOKAI No. Hei 3-17052 discloses 2-methoxyimino-2-[2-(5,6,7,8-tetrahydronaphthalene-2-yloxymethyl)phenyl]-methylacetate (compound No. 1,246) as a specific example of the compounds: 
J. P. KOKAI No. Sho 63-216848 discloses propene derivatives usable for fungicide compositions. Specifically, methyl 3-methoxy-2-[2-(dibenzofuran-2-yloxymethyl)-phenyl]-acrylate (compound No. 189) is given in this patent specification. 
It is known that these compounds are effective in controlling diseases (the effects of controlling insect pests are not described in those specifications). However, the derivatives described therein are utterly different from those of the present invention in that they do not have an alkoxyimino substituent in the polycyclic part thereof. Further, these compounds have no or substantially no penetration and translocation. Under these circumstances, it is demanded to provide an agent for controlling diseases, which has an excellent penetration and translocation.
The object of the present invention is to provide alkoxyimino-substituted bicyclic derivatives having an effect of controlling diseases or insect pests and also an excellent penetration and translocation.
After intensive investigations on agents for controlling diseases, which have an excellent penetration and translocation, the inventors have found that alkoxyimino-substituted bicyclic derivatives having a specific structure have a high penetration and translocation into plants and an excellent effect of controlling diseases and insect pests. The present invention has been completed on the basis of this finding.
The present invention is as follows:
1. An alkoxyimino-substituted bicyclic derivative having the following formula (I) or salt thereof: 
xe2x80x83wherein R1 represents a hydrogen atom, a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C3-C5 alkenyl group, a halogenated C3-C5 alkenyl group, a C3-C5 alkynyl group, a halogenated C3-C5 alkynyl group, a cyano-C1-C6 alkyl group, a C1-C4 alkoxy-C1-C6 alkyl group, a C1-C4 alkylcarbonyl-C1-C6 alkyl group, a C1-C4 alkoxycarbonyl-C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl-C1-C6 alkyl group, a phenyl-C1-C6 alkyl group, or a naphthyl-C1-C6 alkyl group, R2, R3, R4 and R5 independently represent a hydrogen atom, a C1-C3 alkyl group or a halogenated C1-C3 alkyl group,
A represents an oxygen atom, a sulfur atom or C(R)R7, R6 and R7 independently represent a hydrogen atom, a C1-C3 alkyl group or a halogenated C1-C3 alkyl group, n represents 0, 1 or 2,
U, V and W independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C1-C6 alkoxy group, a halogenated C1-C6 alkoxy group, a cyano group or a nitro group,
X and Y independently represent a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a halogenated C1-C3 alkyl group, a C1-C3 alkoxy group, a halogenated C1-C3 alkoxy group, a cyano group or a nitro group,
Z represents C(CO2CH3)xe2x95x90CHR8, C(CO2CH3)xe2x95x90NOCH3, C(CONHCH3)xe2x95x90NOCH3, C(CSNHCH3)xe2x95x90NOCH3, N(CO2CH3)OCH3, N(CONHCH3)OCH3, N(CSNHCH3)OCH3, CH(CO2CH3)OCH3, CH(CONHCH3OCH3 or CH(CSNHCH3)OCH3, and R8 represents a hydrogen atom, a methyl group, an ethyl group or a methoxyl group.
2. A process for producing an alkoxyimino-substituted bicyclic derivative having the formula (I) set forth in above item 1, which comprises reacting a phenol having the formula (II): 
xe2x80x83wherein R1 represents a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C3-C5 alkenyl group, a halogenated C3-C5 alkenyl group, a C3-C5 alkynyl group, a halogenated C3-C5 alkynyl group, a cyano-C1-C6 alkyl group, a C1-C4 alkoxy-C1-C6 alkyl group, a C1-C4 alkylcarbonyl-C1-C6 alkyl group, a C1-C4 alkoxycarbonyl-C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl-C1-C6 alkyl group, a phenyl-C1-C6 alkyl group, or a naphthyl-C1-C6-alkyl group,
R2, R3, R4 and R5 independently represent a hydrogen atom, a C1-C3 alkyl group or a halogenated C1-C3-alkyl group,
A represents an oxygen atom, a sulfur atom or C(R6)R7,
R6 and R7 independently represent a hydrogen atom, a C1-C3 alkyl group or a halogenated C1-C3 alkyl group,
n represents 0, 1 or 2, and
U, V and W independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C1-C6 alkoxy group, a halogenated C1-C6 alkoxy group, a cyano group or a nitro group,
with a phenyl compound having the formula (III): 
xe2x80x83wherein X and Y independently represent a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a halogenated C1-C3 alkyl group, a C1-C3 alkoxy group, a halogenated C1-C3 alkoxy group, a cyano group or a nitro group,
L represents a leaving group,
Z represents C(CO2CH3)xe2x95x90CHR8, C(CO2CH3)xe2x95x90NOCH3, C(CONHCH3)xe2x95x90NOCH3, C(CSNHCH3)xe2x95x90NOCH3, N(CO2CH3)OCH3, N(CONHCH3)OCH3, N(CSNHCH3)OCH3, CH(CO2CH3)OCH3, CH(CONHCH3)OCH3 or CH(CSNHCH3)OCH3, and
R8 represents a hydrogen atom, a methyl group, an ethyl group or a methoxy group.
3. A process for producing an alkoxyimino-substituted bicyclic derivative having the formula (I) set forth in above item 1, which comprises reacting a substituted bicyclic compound having the formula (IV): 
xe2x80x83wherein R2, R3, R4 and R5 independently represent a hydrogen atom, a C1-C3 alkyl group or a halogenated C1-C3 alkyl group,
A represents an oxygen atom, a sulfur atom or C(R6)R7,
R6 and R7 independently represent a hydrogen atom, a C1-C3 alkyl group or a halogenated C1-C3 alkyl group,
n represents 0, 1 or 2,
U, V and W independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C1-C6 alkoxy group, a halogenated C1-C6 alkoxy group, a cyano group or a nitro group,
X and Y independently represent a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a halogenated C1-C3 alkyl group, a C1-C3 alkoxy group, a halogenated C1-C3 alkoxy group, a cyano group or a nitro group,
Z represents C(CO2CH3)xe2x95x90CHR8, C(CO2CH3)xe2x95x90NOCH3, C(CONHCH3)xe2x95x90NOCH3, C(CSNHCH3)xe2x95x90NOCH3, N(CO2CH3)OCH3, N(CONHCH3)OCH3, N(CSNHCH3)OCH3, CH(CO2CH3)OCH3, CH(CONHCH3)OCH3 or CH(CSNHCH3)OCH3, and
R8 represents a hydrogen atom, a methyl group, an ethyl group or a methoxy group, with an amine having the formula (V) or a salt thereof:
R1ONH2xe2x80x83xe2x80x83(V)
xe2x80x83wherein R1 represents a hydrogen atom, a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C3-C5 alkenyl group, a halogenated C3-C5 alkenyl group, a C3-C5 alkynyl group, a halogenated C3-C5 alkynyl group, a cyano-C1-C6 alkyl group, a C1-C4 alkoxy-C1-C6 alkyl group, a C1-C4 alkylcarbonyl-C1-C6 alkyl group, a C1-C4 alkoxycarbonyl-C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl-C1-C6 alkyl group, a phenyl-C1-C6 alkyl group, or a naphthyl-C1-C6 alkyl group.
4. An agent for controlling a disease or an insect pest, comprising the alkoxyimino-substituted bicyclic derivative or salt thereof set forth in above item 1 as an active ingredient.
5. An intermediate having the following formula (II): 
xe2x80x83wherein R1 represents a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C3-C5 alkenyl group, a halogenated C3-C5 alkenyl group, a C3-C5 alkynyl group, a halogenated C3-C5 alkynyl group, a cyano-C1-C6 alkyl group, a C1-C4 alkoxy-C1-C6 alkyl group, a C1-C4 alkylcarbonyl-C1-C6 alkyl group, a C1-C4 alkoxycarbonyl-C1-C6 alkyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl-C1-C6 alkyl group, a phenyl-C1-C6 alkyl group, or a naphthyl-C1-C6 alkyl group,
R2, R3, R4 and R5 independently represent a hydrogen atom, a C1-C3 alkyl group or a halogenated C1-C3 alkyl group,
A represents an oxygen atom, a sulfur atom or C(R6)R7,
R6 and R7 independently represent a hydrogen atom, a C1-C3 alkyl group or a halogenated C1-C3 alkyl group, and
U, V and W independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C1-C6 alkoxy group, a halogenated C1-C6 alkoxy group, a cyano group or a nitro group, and n represents 0, 1 or 2.
6. An intermediate having the following formula (IV): 
xe2x80x83wherein R2, R3, R4 and R5 independently represent a hydrogen atom, a C1-C3 alkyl group or a halogenated C1-C3 alkyl group,
A represents an oxygen atom, a sulfur atom or C(R6)R7,
R6 and R7 independently represent a hydrogen atom, a C1-C3 alkyl group or a halogenated C1-C3 alkyl group,
n represents 0, 1 or 2,
U, V and W independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a halogenated C1-C6 alkyl group, a C1-C6 alkoxy group, a halogenated C1-C6 alkoxy group, a cyano group or a nitro group,
X and Y independently represent a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a halogenated C1-C3 alkyl group, a C1-C3 alkoxy group, a halogenated C1-C3 alkoxy group, a cyano group or a nitro group,
Z represents C(CO2CH3)xe2x95x90CHR8, C(CO2CH3)xe2x95x90NOCH3, C(CONHCH3)xe2x95x90NOCH3, C(CSNHCH3)xe2x95x90NOCH3, N(CO2CH3)OCH3, N(CONHCH3)OCH3, N(CSNHCH3)OCH3, CH(CO2CH3)OCH3, CH(CONHCH3)OCH3 or CH(CSNHCH3)OCH3, and
R8 represents a hydrogen atom, a methyl group, an ethyl group or a methoxy group.
The detailed description will be made on the present invention.
For R1, the C1-C6, preferably C1-C4 alkyl groups include straight or branched alkyl groups such as methyl, ethyl, isopropyl, propyl, n-butyl, isobutyl, s-butyl, n-pentyl, isopentyl and n-hexyl groups.
The halogen atoms in the halogenated C1-C6, preferably C1-C4 alkyl groups include fluorine, chlorine and bromine atoms. Therefore, the halogenated C1-C6 alkyl groups include trifluoromethyl, difluoromethyl, 2-trifluoroethyl, 2-chloroethyl and 2-(4,5-dichloro)hexyl groups.
The C3-C5 alkenyl groups may be either straight or branched. They include allyl, 2-butenyl and 1-methyl-2-propenyl groups. The range of the halogen atoms in the halogenated C3-C5 alkenyl groups is the same as that described above.
The C3-C5 alkynyl groups may be either straight or branched. They include propargyl and 2-butynyl groups. The range of the halogen atoms in the halogenated C3-C5 alkynyl groups is the same as that described above.
The cyano-C1-C6 alkyl groups include cyanomethyl, 2-cyanoethyl and 2-(1-cyano)propyl groups. The C1-C4 alkoxy-C1-C6 alkyl groups include methoxymethyl, 1-ethoxyethyl, dimethoxymethyl and 2,2-diethoxyethyl groups. The C1-C4 alkylcarbonyl-C1-C6 alkyl groups include methylcarbonylmethyl, 1-ethylcarbonylethyl and isopropylcarbonylmethyl group. The C1-C4 alkoxycarbonyl-C1-C6 alkyl groups include methoxycarbonylmethyl, ethoxycarbonylmethyl and 2-ethoxycarbonylethyl groups. The C3-C6 cycloalkyl groups include cyclopropyl and cyclohexyl groups. The C3-C6 cycloalkyl-C1-C6 alkyl groups include cyclopropylmethyl and cyclohexylmethyl groups. The phenyl-C1-C6 alkyl groups (the phenyl group may have at least one of halogens, a cyano, a C1-C4 alkoxy groups and a halogenated C1-C4 alkoxy groups) include benzyl, 3,4-dichlorobenzyl, 4-methoxybenzyl and 4-trifluoromethoxybenzyl groups. The naphthyl-C1-C6 alkyl groups (the naphthyl group may have at least one of halogens, a cyano, a C1-C4 alkoxy groups and a halogenated C1-C4 alkoxy groups) include (1-naphthyl)methyl and (5-chloronaphthyl-2-yl)methyl group.
For R2, R3, R4 and R5, the ranges of the C1-C6 alkyl groups and the halogenated alkyl groups thereof are the same as those described above.
A represents an oxygen atom, a sulfur atom or C(R6)R7 wherein the ranges of R6 and R7 are the same as those of R2, R3, R4 and R5. Preferably, A is an oxygen atom.
n is 0, 1 or 2. When n is 0, the ring structure containing the part in parentheses in the formula (I) is a five-membered ring; and when n is 1, the ring structure containing the part in parentheses in the formula (I) is a six-membered ring.
For X and Y, the ranges of the halogen atoms, C1-C3 alkyl groups and halogenated alkyl groups thereof are the same as those described above. The C1-C3 alkoxy groups or the alkoxy groups in the halogenated alkoxy groups are those having 1 to 3 carbon atom. The C1-C3 alkyl groups in these groups include methyl, ethyl, propyl and isopropyl groups. The C1-C3 alkoxy groups include methoxy, ethoxy, and n-and isopropoxy groups. The halogenated C1-C3 alkoxy groups include difluoromethoxy and 2-chloroethoxy groups.
For U, V and W, the ranges of the halogen atoms, C1-C6 alkyl groups and halogenated alkyl groups are the same as those described above. The C1-C6 alkoxy groups and the alkoxy groups in the halogenated alkoxy groups are those corresponding to the alkyl groups having 1 to 6 carbon atoms. The range of the alkyl groups having 1 to 6 carbon atoms is the same as that described above.
Z represents C(CO2CH3)xe2x95x90CHR3, C(CO2CH3)xe2x95x90NOCH3, C(CONHCH3)xe2x95x90NOCH3, C(CSNHCH3)xe2x95x90NOCH3, N(CO2CH3)OCH3, N(CONHCH3)OCH3, N(CSNHCH3)OCH3, CH(CO2CH3)OCH3, CH(CONHCH3)OCH3 or CH(CSNHCH3)OCH3, and R3 represents a hydrogen atom, methyl group, ethyl group or methoxy group.
The alkoxyimino-substituted bicyclic derivatives may be in the form of salts thereof. The salts are, for example, sodium salts and potassium salts.
The alkoxyimino-substituted bicyclic derivatives of the present invention can be produced each in the form of a mixture of isomers such as geometrical isomers [(E)/(Z)], optical isomers and diastereomers. When the alkoxyimino-substituted bicyclic derivatives of the present invention are produced in the form of the isomer mixtures, they can be divided into respective isomers by an ordinary method such as the recrystallization or chromatography. When the geometrical isomers [(E)/(Z)] of Z is formed, the (E) isomer is preferred in view of the effect of controlling diseases or insect pests in many cases, and as for the geometrical isomers [(E)/(Z)] of xe2x95x90Nxe2x80x94OR1, both isomers exhibit the excellent controlling effects. .
The alkoxyimino-substituted bicyclic derivatives of general formula (I) or salts thereof can be easily produced by, for example, the following method: 
In process (1), the compounds of Formula (I) are produced from compounds of Formula (VI) by a well-known method. As for the compounds of Formula (VI), for example, 3-oxobenzofuran can be produced by a method disclosed in WO 89/05289, 4-oxochroman can be produced by a method disclosed in J. Org. Chem. 59: 1216-1218 (1994) or WO 96/06081, and 1-oxo-indane and 1-oxo-tetrahydronaphthalene can be produced by a method disclosed in WO 91/14674 or U.S. Pat. No. 5,128,362.
The compounds of Formula (II) can be produced by reacting a compound of Formula (VI) with a hydroxyamine compound of Formula (V) or an acid-addition salt (such as hydrochloride or bromate) thereof.
The hydroxyamine compound of Formula (V) or its acid-addition salt is used in an amount of, for example, 1 to 5 equivalents, preferably 1 to 1.5 equivalents, per equivalent of the compound of Formula (VI).
The acids usable for forming the acid-addition salts of the hydroxyamine compounds include inorganic acids such as hydrochloric acid, bromic acid and sulfuric acid, and organic acids such as p-toluenesulfonic acid (tosylic acid).
This reaction can be conducted in a solvent (such as methanol, ethanol or toluene) or in a two-phase (such as toluene/water) system. It is advantageous in some cases to add a base (such as triethylamine, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide or potassium hydroxide) to the reaction mixture. The base is used in an amount of usually 0.05 to 5 equivalents, preferably 1 to 1.5 equivalents, per equivalent of the compound of Formula (VI).
The reaction temperature ranges from xe2x88x9220xc2x0 C. to a reflux temperature of the solvent, preferably 0 to 50xc2x0 C., and the reaction time is, for example, 0.5 to 72 hours, preferably 0.5 to 12 hours.
The compounds of Formula (I) can be produced by reacting a compound of Formula (II), thus obtained, with a compound of Formula (III).
The compounds of Formula (III) can be produced by a well-known method. L in Formula (III) is a leaving group such as chlorine atom, bromine atom, p-toluenesulfonate group, methanesulfonate group or trifluoromethanesulfonate group.
Compounds of Formula (III) wherein Z is C(COOCH3)xe2x95x90CHR3 can be produced by a method disclosed in J. P. KOKAI No. Hei 5-213815, those wherein Z is C(COOCH3)xe2x95x90NOCH3 can be produced by a method disclosed in EP-386561A; those wherein Z is CH(COOCH3)OCH3 or CH(CONHCH3)OCH3 can be produced by a method disclosed in WO 95/27693; and those wherein Z is N(COOCH3)OCH3 or N(CONHCH3)OCH3 can be produced by a method disclosed in WO 93/15046.
In the reaction of a compound of Formula (II) with a compound of Formula (III), the former is used in an amount of, for example, 0.5 to 3 equivalents, preferably 0.8 to 1.5 equivalents, per equivalent of the latter.
The reaction of compound (II) with compound (III) can be conducted in the presence of a base (such as triethylamine, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide, potassium hydroxide or sodium hydride) in a solvent (such as acetone, acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone or pyridine). The base is used in an amount of 1 to 5 equivalents, preferably 1 to 1.5 equivalents, per equivalent of the compound of Formula (III). It is advantageous in some cases to add a catalyst such as tris-(3,6-dioxoheptyl)amine to the reaction mixture.
The reaction temperature is suitably selected in the range of xe2x88x9220xc2x0 C. to a refluxing temperature of the solvent, preferably 0 to 50xc2x0 C., and the reaction time is 0.5 to 72 hours, preferably 0.5 to 12 hours. 
In process (2), each compound of Formula (IV) can be produced by reacting a compound of Formula (VI) with a compound of Formula (III). The compounds of Formula (I) can be produced by reacting a compound of Formula (IV) with a hydroxyamine compound of Formula (V) or an acid addition salt (such as hydrochloride or bromate).
The hydroxyamine compound of Formula (V) or acid addition salt thereof is used in an amount of, for example, 1 to 5 equivalents, preferably 1 to 1.5 equivalents, per equivalent of the compound of Formula (IV).
This reaction can be conducted in a solvent (such as methanol, ethanol or toluene) or in a two-phase (such as toluene/water) system. It is advantageous in some cases to add a base (such as triethylamine, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide or potassium hydroxide) to the reaction mixture. The base is used in an amount of usually 1 to 5 equivalents, preferably 1 to 1.5 equivalents, per equivalent of the compound of Formula (IV).
The reaction temperature is suitably selected in the range of from xe2x88x9220xc2x0 C. to a reflux temperature of the solvent, preferably 0 to 50xc2x0 C., and the reaction time is, for example, 0.5 to 72 hours, preferably 0.5 to 12 hours. 
In this process, compounds of Formula (I-1) can be produced by reacting compounds of Formula (VII) with monomethylamine. Monomethylamine is used in an amount of, for example, 1 to 10 equivalents, preferably 1 to 3 equivalents, per equivalent of a compound of formula (VII).
The reaction is preferably conducted in a solvent (such as methanol, ethanol, tetrahydrofuran, diethyl ether or water) at a temperature suitably selected in the range of from xe2x88x9220xc2x0 C. to a reflux temperature of the solvent, preferably 0 to 50xc2x0 C., for a reaction time of, for example, 0.5 to 72 hours, preferably 0.5 to 12 hours.
Compounds of Formula (I-2) can be produced by sulfurizing compounds of Formula (I-1). The sulfurizing agent (such as phosphorus pentasulfide or Lawesson""s reagent) is used in an amount of, for example, 1 to 5 equivalents, preferably 1 to 2 equivalents, per equivalent of the compound of Formula (I-1).
The reaction is preferably conducted in a solvent (such as toluene, xylene or pyridine) at a temperature suitably selected in the range of from room temperature to a reflux temperature of the solvent, preferably 80 to 150xc2x0 C., for a reaction time of, for example, 0.5 to 72 hours, preferably 0.5 to 12 hours. 
In this process, compounds of Formula (VIII) can be produced by reacting a compound of Formula (II) with methyl (2-bromomethylphenyl)glyoxylate.
The compounds of Formula (I-3) can be produced by reacting a compound of Formula (VIII) with methoxyamine hydrochloride.
The amount of methoxyamine hydrochloride is used in an amount of, for example, 1 to 10 equivalents, preferably 1 to 3 equivalents, per equivalent of the compound of Formula (VIII).
This reaction can be conducted in a solvent (such as methanol, ethanol or toluene) or in two-phase (such as toluene/water) system. It is advantageous in some cases to add a base (such as triethylamine, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium. hydrogencarbonate, sodium hydroxide or potassium hydroxide) to the reaction mixture. The base is used in an amount of, for example, 1 to 10 equivalents, preferably 1 to 3 equivalents, per equivalent of the compound of Formula (VIII).
The reaction temperature is suitably selected in the range of from xe2x88x9220xc2x0 C. to a reflux temperature of the solvent, preferably 0 to 50xc2x0 C., and the reaction time is, for example, 0.5 to 72 hours, preferably 0.5 to 12 hours.
The compounds of Formula (I-4) can be produced by reacting a compound of Formula (VIII) with a compound of Formula (IX) (Wittig reagent or Wittig/Horner reagent) by a known method (such as a method disclosed in J. P. KOKAI No. Hei 5-213815).
The compound of Formula (VIII) is used in an amount of, for example, 0.1 to 3 equivalents, preferably 0.2 to 1.5 equivalents, per equivalent of the compound of Formula (IX).
The reaction can be conducted in the presence of a base (such as sodium methoxide, potassium t-butoxide or sodium hydride) in a solvent (such as tetrahydrofuran, diethyl ether, dimethyl sulfoxide or dimethylformamide). The base is used in an amount of, for example, 1 to 5 equivalents, preferably 1 to 1.5 equivalents, per equivalent of the compound of Formula (IX).
The reaction temperature is suitably selected in the range of from xe2x88x9220xc2x0 C. to a reflux temperature of the solvent, preferably xe2x88x9210 to 30xc2x0 C., and the reaction time is, for example, 0.5 to 72 hours, preferably 0.5 to 12 hours.
The compounds of Formula (I-5) can be produced by reacting a compound of Formula (VIII) with a reducing agent and then methylating the reaction product.
The reducing agent is one usually used for the reduction of ketones, such as sodium borohydride, lithium borohydride or lithium aluminum hydride. The reducing agent is used in an amount of, for example, 0.5 to 5 equivalents, preferably 1 to 1.5 equivalents, per equivalent of the compound of Formula (VIII).
The reaction is preferably conducted in a solvent (such as methanol, ethanol, tetrahydrofuran, diethyl ether or water) or in a two-phase system (such as ethyl acetate/water) at a temperature suitably selected in the range of from xe2x88x9220xc2x0 C. to a reflux temperature of the solvent, preferably 0 to 50xc2x0 C., for 0.5 to 72 hours, preferably 0.5 to 6 hours.
A compound of Formula (I-5) can be obtained by methylating the resultant alcohol compound.
The methylating agents usable herein are, for example, methyl chloride, methyl bromide, methyl iodide and dimethylsulfuric acid. The methylating agent is used in an amount of, for example, 0.5 to 5 equivalents, preferably 0.8 to 1.5 equivalents, per equivalent of the obtained alcohol compound.
The reaction can be conducted by using a base (such as sodium methoxide, potassium t-butoxide, sodium hydroxide, potassium hydroxide or sodium hydride) in an inert solvent (such as acetonitrile, tetrahydrofuran, diethyl ether, dimethylformamide or N-methylpyrrolidone). The base is used in an amount of, for example, 1 to 5 equivalents, preferably 1 to 1.5 equivalents, per equivalent of the compound of Formula (III).
The reaction temperature is suitably selected in the range of from xe2x88x9220xc2x0 C. to a reflux temperature of the solvent, preferably 0 to 50xc2x0 C., and the reaction time is, for example, 0.5 to 72 hours, preferably 0.5 to 12 hours. 
In this process, compounds (i) can be produced by, for example, reacting a compound of Formula (II) with o-nitrobenzyl bromide.
Compound (ii) can be obtained by reacting compound (i) with ammonium chloride in the presence of zinc [Organic Syntheses Coll. Vol. III, p. 668 (1955)]. Then compound (ii) is reacted with methyl chloroformate to obtain compound (iii). A compound of Formula (I-6) can be obtained by treating compound (iii) in the same manner as that of the methylation in production process (4). 
In this process, compounds (iv) can be obtained by reacting compound (ii) with, for example, methyl isocyanate. Compounds of Formula (I-7) can be obtained by methylating compounds (iv) in the same manner as that of the methylation in production process (4). 
In this process, compound (v) can be obtained by an ordinary method such as a method which comprises formylating compound (ii) with formic acid and acetic anhydride. Compound (vi) can be obtained by methylating compound (v) in the same manner as that of preparation process (4). Then, compound (vi) is hydrolyzed to obtain compound (vii), which is reacted with thiophosgene, and the product is reacted with monomethylamine or methyl thioisocyanate to obtain a compound of Formula (I-8).
The compounds of the present invention even in an extremely low concentration are effective on various harmful insect pests. The insect pests which can be controlled by the compounds of the present invention include, for example, insects of the order of beetles such as scarab beetles, leaf beetles, 28-spotted lady beetles (Epilachna sparsa orientalis) and rice water weevil (Lissorhoptrus oryzophilus); lepidopterons such as cabbage army worms (Mamestra brassicae), common cabbage worms (Pieris rapae crucivora), diamond back moth (Plutella xylostera), beet semi-looper (Autographa nigrisigna), leaf folders and rice borers; insects of Hemiptera such as plant hoppers, leaf hoppers, white flies, aphides and coccidia; thrips such as yellow tea thrips (Scirtothrips dorsalis) and Thrips palmi; sanitary insect pests such as mosquitoes, flies, cockroaches, fleas and lice, stored grain insect pests, clothes moths, house insect pests, plant parasitic nematodes such as root-knot nematodes and root-lesion nematodes (Pratylenchus paratensis); and plant parasitic spider mites such as two-spotted spider mite (Tetranychus urticae), kanzawa spider mite (Tetranychus kanzawai) and citrus red mite (Panonychus citri) They are also effective on soil insect pests. The term xe2x80x9csoil insect pestsxe2x80x9d herein include gastropods such as slugs and snails; and wood lice (isopods) such as pill bugs and sow bugs. Further, they are effective on plant parasitic spider mites which are resistant to Dicofol and organophosphorus pesticides, and aphids and houseflies resistant to organophosphorus pesticides.
The plant diseases which can be controlled by the compounds of the present invention include, for example, Rice blast (Pyricularia oryzae), Rice sheath blight (Rhizoctonia solani), Rice brown spot (Chochliobolus miyabeanus), Wheat eye spot (Pseudocercosporella herpotrichoides), powdery mildews of various host plants such as Erysiphe graminis, Sphaerotheca fuliginea and Uncinula necator, Oat crown rust (Puccinia coronata) and rust of other plants, Botrytis cinerea of Grape and gray-mold of other plants, Cucumber stem rot (Sclerotinia sclerotiorum) and stem rot of other plants, Poteto late blight (Phytophthora infestans), and late blight and phytophthora diseases of other plants, downy mildew of various plants such as Pseudoperonospora cubensis and Plasmopara viticola, scab of various plants such as Venturia inaequalis and Venturia nashicola, Alternaria diseases of varius plants such as Alternaria mali and Alternaria kikuchiana, Monilinia disease of varius plants such as Apple blossom blight (Monilinia mali) and Peach brown rot (Monilinia fructicola), Citrus melanose (Diaporthe citri) and Citrus penicillium rot (Penicillium italicum). The compounds of the present invention have extremely excellent effects of controlling these diseases and, in particular, the excellent effects of them can be exhibited even in a low concentration.
The agents of the present invention for controlling diseases and insect pests have a remarkable effect of controlling the diseases and insect pests which harm paddy field crops, non-paddy field crops, fruit trees, vegetables and other crops as well as flowering plants. They are used for treating water in paddy fields, and also stems, leaves, soils, seeds and bulbs of fruit trees, vegetables and other crops as well as flowering plants in paddy fields and non-paddy fields before the diseases or insect pests appear or when they are found. The intended effects of the agents of the present invention for controlling diseases and insect pests are thus exhibited.
The concentration and amount of the compounds of the present invention to be used cannot indiscriminately be limited because they vary depending on the crops to be treated, method of the application, form of the preparation and dose. However, in the treatment of stems and leaves, the concentration of the active ingredient is usually 0.1 to 10,000 ppm, desirably 1 to 2,000 ppm. The concentration can be suitably changed depending on the form of the preparation, application method, purpose, period and site of the application, and state of the disease or insect pests. For example, in controlling aquatic insect pests, the range of the concentration of the effective ingredient in water is below the above-described range because the insect pests can be controlled even when the preparation having the concentration in the above-described range is applied. As for the dose per a unit area, the compound to be used as the active ingredient is used in an amount of about 0.1 to 5,000 g, preferably 10 to 1,000 g, for every 10 a, of the field. However, in particular cases, the dose can be not within the range.
The compounds of the present invention can be mixed with or used in combination with other pesticides such as insecticides, acaricides, nematicides and fungicides to exhibit more excellent effects. They can also be mixed with or used in combination with an antiviral agent, attractant, herbicide, plant growth regulator or the like.
The compounds usable as active ingredients of the above-described insecticides, acaricides and nematicides include, for example, organophosphoric ester compounds such as O-(4-bromo-2-chlorophenyl) O-ethyl-S-propylphosphorothioate (common name: Profenofos), O-(2,2-dichlorovinyl) O,O-dimethylphosphate (common name: Dichlorvos), O-ethyl O-[3-methyl-4-(methylthio)phenyl] N-isopropylphosphoroamidate (common name: Fenamiphos), O,O-dimethyl O-(4-nitro-m-tolyl)phosphorothioate (common name: Fenitrothion), O-ethyl O-(4-nitrophenyl)phenylphosphonothioate (common name: EPN), O,O-diethyl O-(2-isopropyl-6-methylpyrimidine-4-yl)phosphorothioate (common name; Diazinon), O,O-dimethyl O-(3,5,6-trichloro-2-pyridyl)phosphorothioate (common name: Chlorpyrifos-methyl), O,S-dimethyl N-acetylphosphoroamidothioate (common name: Acephate), O-(2,4-dichlorophenyl), O-ethyl S-propylphosphorodithioate (common name: Prothiofos) and (RS)-S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidine-3-ylphosphonothioate (common name: Fosthiazate);
carbamate compounds such as 1-naphthyl N-methylcarbamate (common mane: Carbaryl), 2-isopropoxyphenyl N-methylcarbamate (common name: Propoxur) 2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime (common name: Aldicarb), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate (common name: Carbofuran), dimethyl N,Nxe2x80x2-[thiobis(methylimino)carbonyloxy)]bisethanimidothioate (common name: Thiodicarb), S-methyl N-(methylcarbamoyloxy)thioacetimidate (common name: Methomyl), N,N-dimethyl-2-methylcarbamoyloxyimino-2-(methylthio)acetamide (common name: Oxamyl), 2-(ethylthiomethyl)phenyl N-methylcarbamate (common name; Ethiofencarb), 2-dimethylamino-5,6-dimethylpyrimidinnne-4-yl N,N-dimethylcarbamate (common name: Pirimicarb) and 2-sec-butylphenyl N-methylcarbamate (common name: Fenobucarb);
Nereistoxin derivatives such as S,Sxe2x80x2-2-dimethylaminotrimethylene bis(thiocarbamate) (common name: Cartap) and N,N-dimethyl-1,2,3-trithian-5-ylamine (common name: Thiocyclam);
organochlorine compounds such as 2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol (common name: Dicofol) and 4-chlorophenyl-2,4,5-trichlorophenyl sulfone (common name: Tetradifon);
organometallic compounds such as bis[tris(2-methyl-2-phenylpropyl)tin] oxide (common name: Fenbutatin Oxide); pyrethroid compounds such as (RS)-xcex1-cyano-3-phenoxybenzyl(RS)-2-(4-chlorophenyl)-3-methylbutyrate (common name: Fenvalerate), 3-phenoxybenzyl(IRS)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (common name: Permethrin), (RS)-xcex1-cyano-3-phenoxybenzyl(IRS)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (common name: Cypermethrin), (S)-xcex1-cyano-3-phenoxybenzyl(IR)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (common name: Deltamethrin), (RS)-xcex1-cyano-3-phenoxybenzyl(IRS)-cis, trans-3-(2-chloro-3,3,3-trifluoropropenyl)-2, 2-dimethylcyclopropanecarboxylate (common name: Cyhalothrin), 4-methyl-2,3,5,6-tetrafluorobenzyl-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate (common name: Tefluthrin) and 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether (common name: Ethofenprox);
benzoylurea compounds such as 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (common name: Diflubenzuron), 1-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl] -3-(2,6-difluorobenzoyl)urea (common name: Chlorfluazuron), 1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea (common name: Teflubenzuron);
juvenile hormone-like compounds such as isopropyl (2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate (common name: Methoprene);
pyridazinone compounds such as 2-t-butyl-5-(4-t-butylbenzylthio)-4-chloro-3(2H)-pyridazinone (common name: Pyridaben);
pyrazole compounds such as t-butyl 4-[(1,3-dimethyl-5-phenoxypyrazole-4-yl)methyleneaminoxymethyl]benzoate (common name: Fenpyroximate);
nitro compounds such as 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidine-2-ylideneamine (common name: Imidacloprid), 1-[N-(6-chloro-3-pyridylmethyl)-N-ethylamino]-1-methylamino-2-nitroethylene (European Patent Publication No. 302389), 2-methylamino-2-[N-methyl-N-(6-chloro-3-pyridylmethyl)amino-1-1-nitroethylene (European Patent Publication No. 302389), 1-(6-chloro-3-pyridylmethyl)amino- 1-dimethylamino-2-nitroethylene (European Patent Publication No. 302389), 1-(6-chloro-3-pyridylmethyl)-2-(1-nitro-2-llylthioethylidene)imidazolidine (European Patent Publication No. 437784), 1-(6-chloro-3-pyridylmethyl)-2-(I-nitro-2-ethylthioethylidene)imidazolidine (European Patent Publication No. 437784), 1-(6-chloro-3-pyridylmethyl)-2-(1-nitro-2-xcex2-methylallylthioethylidene)imidazolidine (European Patent Publication No. 437784), 1-(6-chloro-3-pyridylmethyl)-3-methyl-2-nitroguanidine (European Patent Publication No. 383091), 1-(6-chloro-3-pyridylmethyl)-3,3-dimethyl-2-nitroguanidine (European Patent Publication No. 383091), 3-(6-chloro-3-pyridylmethyl)-2-nitromethylene-thiazolidine (European Patent Publication No. 192060), 1-(6-chloro-3-pyridylmethyl)-2-(nitromethylene)imidazolidine (European Patent Publication No. 163855), 6-(6-chloro-3-pyridylmethylamino)-1,3-dimethyl-5-nitro-1,2,3,4-tetrahydropyrimidine (European Patent Publication No. 366085) and 1-(6-chloro-3-pyridylmethyl)-5-nitro-3-methyl-6-methylamino- 1,2,3,4-tetrahydropyrimidine (European Patent Publication No. 366085);
dinitro compounds, organosulfur compounds, urea compounds, triazine compounds, hydrazine compounds and other compounds such as 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazine-4-on (common name: Buprofezin), trans- (4-chlorophenyl) -N-cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide (common name: Hexythiazox), N-methylbis(2,4-xylyliminomethyl)amine (common name: Amitraz), Nxe2x80x2-(4-chloro-o-tolyl)-N,N-dimethylformamidine (common name: Chlordimeform) and (4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl)propyl)(dimethyl)silane (common name: Silafluofen). Further, the compounds of the present invention may also be used in mixture or combination with microbial pesticides such as BT and insect pathogenic viruses, and also antibiotics such as avermectin and milbemycin.
Compounds usable as the active ingredients of the fungicides include pyrimidinamine compounds such as 2-anilino-4-methyl-6-(1-propinyl)pyrimidine (common name- Mepanipyrim) and 4,6-dimethyl-N-phenyl-2-pyrimidinamine (common name: Pyrimethanil);
azole compounds such as 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazole-1-yl)butanone (common name: Triadimefon), 1-(biphenyl-4-yloxy)-3,3-dimethyl-1-(1H,1,2,4-triazole-1-yl)butane-2-ol (common name: Bitertanol), 1-[N-(4-chloro-2-trifluoromethylphenyl]-2-propoxyacetimidoyl]imidazole (common name: Triflumizole), 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolane-2-ylmethyl]-1H-1,2,4-triazole (common name: Etaconazole), 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane-2-ylmethyl]-1H-1,2,4-triazole (common name: Propiconazole), 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole (common name: Penconazole), bis(4-fluorophenyl)(methyl) (1H-1,2,4-triazole-1-ylmethyl)silane (common name: Flusilazole), 2-(4-chlorophenyl)-2-(1H, 1,2,4-triazole-1-ylmethyl)hexanenitrile (common name: Myclobutanil), (2RS,3RS)-2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazole-1-yl)butane-2-ol (common name: Cyproconazole), (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazole- 1-ylmethyl)pentane-3-ol (common name: Terbuconazole), (RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazole-1-yl)hexane-2-ol (common name: Hexaconazole), (2RS, 5RS)-5-(2,4-dichlorophenyl)tetrahydro-5-(1H-1,2,4-triazole-1-ylmethyl)-2-furyl 2,2,2-trifluoroethyl ether (common name: Furconazole-cis) and N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide (common name: Prochloraz);
quinoxaline compounds such as 6-methyl-1,3-dithiolo[4,5-b]quinoxaline-2-on (common name: Quinomethionate); dithiocarbamate compounds such as manganese ethylene bis(dithiocarbamate) polymer (common name: maneb), zinc ethylene bis(dithiocarbamate) polymer (common name: zineb), complex of zinc with manganese ethylene bis(dithiocarbamate) (maneb) (common name: Mancozeb), dizinc bis(dimethyldithiocarbamato)ethylene bis(dithiocarbamate) (common name: Polycarbamate) and zinc propylene bis(dithiocarbamate) polymer (common name: Propineb);
organochlorine compounds such as 4,5,6,7-tetrachlorophthalide (common name: Fthalide), tetrachloroisophthalonitrile (common name: Chlorothalonil) and pentachloronitrobenzene (common name: Quintozene); benzimidazole compounds such as methyl 1-(butylcarbamoyl)benzimidazole-2-yl carbamate (common name: Benomyl), dimethyl 4,4xe2x80x2-(o-phenylene)bis(3-thioallophanate) (common name: Thiophnate-Methyl) and methyl benzimidazole-2-ylcarbamate (common name: Carbendazim);
Pyridinamine compounds such as 3-chloro-N-(3-chloro-2,6-dinitro-4-xcex1,xcex1,xcex1-trifluorotolyl)-5-trifluoromethyl-2-pyridinamine (common name: Fluazinam); cyanoacetamide compounds such as 1-(2-methoxyiminoacetyl)-3-ethylurea (common name: Cymoxanil);
phenylamide compounds such as methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate (common name: Metalaxyl), 2-methoxy-N-(2-oxo-1,3-oxazolidine-3-yl)aceto-2xe2x80x2,6xe2x80x2-xylidide (common name: Oxadixyl), (xc2x1)-xcex1-2-chloro-N-(2,6-xylylacetamido)-xcex3-butyrolactone (common name: Ofurace), methyl N-phenylacetyl-N-(2,6-xylyl)-DL-alaninate (common name: Benalaxyl), methyl N-(2-furoyl)-N-(2,6-xylyl)-DL-alaninate (common name: Furalaxyl) and (xc2x1)-xcex1-[N-(3-chlorophenyl)cyclopropanecarboxamido]-xcex3-butyrolactone (common name: Cyprofuram);
sulfenic acid compounds such as N-dichlorofluoromethylthio-Nxe2x80x2, Nxe2x80x2-dimethyl-N-phenylsulfamide (common name: Dichlofluanid); copper compounds such as cupric hydroxide (common name: cupric hydroxide) and copper 8-quinolinolate (common name: Oxine-Copper);
isoxazole compounds such as 5-methylisoxazole-3-ol (common name: Hydroxyisoxazole); organophosphorus compounds such as aluminum tris(ethylphosphonate) (common name: Fosetyl-aluminum), O-2,6-dichloro-p-tolyl-O,O-dimethylphosphorothioate (common name: Tolcofos-methyl), S-benzyl O,O-diisopropyl phosphorothioate, O-ethyl S,S-diphenylphosphorodithioate and aluminum ethyl hydrogenphosphonate;
N-halogenothioalkyl compounds such as N-(trichloromethylthio)cyclohex-4-en-1,2-dicarboximide (common name: Captan), N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-en-1,2-dicarboximide (common name: Captafol) and N-(trichloromethylthio)phthalimide (common name: Folpet);
dicarboxyimide compounds such as N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide (common name: Procymidone), 3-(3,6-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide (common name: Iprodione) and (RS)-3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dion (common name: Vinclozlin);
benzanilide compounds such as xcex1,xcex1,xcex1-trifluoro-3xe2x80x2-isopropoxy-o-toluanilide (common name: Flutolanil) and 3xe2x80x2-isopropoxy-o-toluanilide (common name: Mepronil); benzamide compounds such as 2-(1,3-dimethylpyrazole-4-ylcarbonylamino)-4-methyl-3-pentenenitrile (a compound described in British Patent No. 2,190,375) and xcex1-(nicotinylamino)-(3-fluorophenyl)acetonitrile (a compound described in J. P. KOKAI No. Sho 63-135364);
piperazine compounds such as N,Nxe2x80x2-[piperazine-1,4-diylbis(trichloromethyl)methylene]diformamide (common name: Triforine); pyridine compounds such as 2xe2x80x2,4xe2x80x2-dichloro-2-(3-pyridyl)acetophenone O-methyloxime (common name: Pyrifenox);
carbinol compounds such as (xc2x1)-2,4xe2x80x2-dichloro-xcex1-(pyrimidine-5-yl)benzhydryl alcohol (common name: Fenarimol), (xc2x1)-2,4xe2x80x2-difluoro-xcex1-(1H-1,2,4-triazole-1-5 ylmethyl)benzhydryl alcohol (common name: Flutriafol); piperidine compounds such as (RS)-1-[3-(4-tert-butylphenyl)-2-methylpropyllpiperidine (common name: Fenpropidine); morpholine compounds such as (xc2x1)-cis-4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine (common name: Fenpropimorph);
organotin compounds such as triphenyltin hydroxide (common name: Fentin hydroxide): triphenyltin acetate (common name: Fentin acetate); urea compounds such as 1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea (common name: Pencycuron);
cinnamic acid compounds such as (E,Z)4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloyl]morpholine (common name: Dimethomorph); phenyl carbamate compounds such as isopropyl 3,4-diethoxycarbanylate (common name: Diethofencarb);
cyanopyrrole compounds such as 3-cyano-4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole (common name: Fludioxonil) and 3-(2xe2x80x2,3xe2x80x2-dichlorophenyl)-4-cyanopyrrole (common name: Fenpiclonil); anthraquinone compounds; crotonic acid compounds; and antibiotics.
The weight ratio of the alkoxyimino-substituted bicyclic derivative of above Formula (I) or its salt to the other component to be used in the form of a mixture or in combination with the former is usually 1:300 to 300:1, desirably 1:100 to 100:1. Particularly when the benzyloxybenzene derivative is used in the form of a mixture thereof with a pyrimidinamine compound, organochlorine compound, pyridinamine compound or cyanopyrrole compound, an excellent effect of controlling various gray molds can be expected.
When the alkoxyimino-substituted bicyclic derivatives or salts thereof of the present invention are used in practice, each of them is usually mixed with a powder, solid carrier, solvent, surfactant and other adjuvants for the preparation to form an emulsion, aqueous solution, microemulsion, wettable powder, dust, aqueous or oily suspension, water-dispersible granule, water-soluble powder or microcapsules and others. These preparations contain 0.002 to 80% by weight, preferably 0.01 to 70% by weight, of the above-described compound.
The solid carriers include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut shell powder, urea, ammonium sulfate, synthetic silicic acid hydrate and others.
The solvents are, for example, aromatic and aliphatic hydrocarbons such as xylene, naphthas, methylnaphthalene, paraffins and machine oil; alcohols such as isopropanol, butanol, propylene glycol, ethylene glycol, cellosolve and carbitol; ketones such as acetone, cyclohexanone and isophorone; vegetable oils such as soybean oil and cotton seed oil; dimethyl sulfoxide; N,N-dimethylformamide; N-methylpyrrolidone; acetonitrile; water and others.
The surfactants used for emulsification, dispersion, wetting or the like include anionic surfactants such as lignin sulfonates, alkylnaphthalenesulfonates, naphthalenesulfonates/formaldehyde condensates, alkylsulfates, alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates, polyoxyethylene alkylaryl ether sulfates (sulfonates or phosphates), polyoxyethylene alkyl ether sulfates (phosphates or sulfonates), and polyoxyethylene styrenated and benzylated phenyl ether phosphoric acid or phosphates (sulfates, sulfonates); and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene fatty acid esters, polyoxyethylene/polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene styrenated or benzylated phenyl ethers.
Other adjuvants include alginates, polyvinyl alcohols, acacia gum, carboxymethylcellulose, Xantham gum, Welan gum, isopropyl hydrogen phosphate, etc.
A wettable powder, which is a typical example of the preparations, can be prepared by mixing about 5 to 50 parts by weight of an alkoxyimino-substituted bicyclic derivative or a salt thereof of the present invention with 2 to 5 parts by weight of an anionic surfactants and solid carriers in an amount sufficient for making the whole amount 100 parts by weight, and pulverizing the mixture.
A dust can be prepared by mixing 0.01 to 10 parts by weight of an alkoxyimino-substituted bicyclic derivative or a salt thereof of the present invention with 0.1 to 0.5 part by weight of the above-surfactants, oils and adjuvants and fine mineral powders selected from among solid carriers.
An emulsifiable concentrate can be prepared by mixing 1 to 70 parts by weight of an alkoxyimino-substituted bicyclic derivative or a salt thereof of the present invention with 5 to 15 parts by weight of non-ionic surfactants, 1 to 10 parts by weight of anionic surfactants and a pharmaceutically acceptable solvent(s) in an amount sufficient for making the whole amount 100 parts by weight.
An aqueous suspension can be prepared-by mixing 5 to 50 parts by weight of an alkoxyimino-substituted bicyclic derivative or a salt thereof of the present invention with 1 to 5 parts by weight of a non-ionic surfactant or anionic surfactant and water in an amount sufficient for making the whole amount 100 parts by weight, then wet-milling (grinding) the above mixture until the particle size has been reduced to 0.1 to 3 xcexcm, preferably 0.5 to 2 xcexcm, and mixing the obtained mixture with 0.1 to 1 part by weight of thickening agent(s), and other additives.
A water-dispersible granule comprises granules composed of 5 to 50 parts by weight of a finely pulverized alkoxyimino-substituted bicyclic derivative or the salt thereof of the present invention, 90 to 40 parts by weight of an inorganic salt and/or fine mineral powder selected from among the solid carriers, 0.1 to 5 parts by weight of a binder and 5 to 10 parts by weight of surfactants. When the granule is fed into water, it is rapidly disintegrated and dispersed therein.